Polyvinyl carbazole composition



l atented Feb. 6, 1951 POLYVINYL CARBAZOLE COMPOSITION Warren F. Busse, Easton, Pa., assignor to General Aniline & Film Corporation, New York, N. Y., a corporation of Delaware No Drawing. Application October 12, 1945, Serial No. 622,083

The present invention relates to a novel dielectric material comprising a mixture of a polymeric N-vinyl pyrrole compound and a powdered solid inorganic compound having a dielectric constant higher than 10, such as a wide variety of titanium compounds, for instance rutile type titanium dioxide and numerous titanates, such as the alkaline earth metal titanates. This novel dielectric material possesses a unique combination of properties, electrical and physical, not possessed by dielectric materials which have here tofore been available. Thus, it not only has desirable electric properties, such as a high dielectric constant and a low power factor, but in addition, has desirable physical properties which greatly facilitate its use as a practical dielectric material and which are not possessed by other dielectric materials which may have the high dielectric constant possessed by the materials of this invention. This combination of properties,

. electrical and physical, provides a novel material having a wide field of use in the arts.

The polymeric N-vinyl pyrrole compounds, which are one component of the novel dielectric material of this invention, have found important uses in the electrical arts, since they possess many properties which are of value in this field. Thus, they have a low power factor and, in addition, possess a relatively high heat distortion point which makes them suitable for use at relatively high temperatures, and also possess satisfactory mechanical properties. However, the dielectric constant of such polymeric N-vinyl pyrrole compounds averages slightly less than 3, so that they are unsiutable for use as a dielectric material in applications which require a compound having a higher dielectric constant.

Numerous titaniferous compounds which have a1 dielectric constant higher than are known and have found important applications as solid dielectric materials of high dielectric constant and stable over 100 0., generally in the form of fired bodies of titanium dioxide (rutile), or other titaniferous compounds, such as the alkaline earth metal titanates. However, their usefulness has been limited by the fact that they cannot be fired to close tolerances, as is typical of ceramics, and after firing, can be shaped only by expensive grinding processes. Not only are such titanate dielectrics diflicult to shape, but it is impossible to produce them in a form satisfactory for many uses. Thus, it is manifestly impossible to produce uniform sheets of such materials.

-It has now been found that by incorporatin titanium compounds having-a dielectric constant 1 Claim. (Cl. 2150-33-8) higher than 10, in polymeric N-vinyl pyrrole compounds, the resulting mixture hasphysical properties which permits it to be readily cast or molded in accordance with the usual procedures for casting or shaping organic polymers, and shaped articles produced from such mixtures not only have physical properties of flexural strength and high heat distortion temperature common to shaped articles produced from polymeric N- vinyl pyrrole compounds containing inorganic fillers but, in addition, have a greatly increased dielectric constant which has not heretofore been obtainable in combination with the other desirable physical properties. By control of the composition of the mixture and selection of the titaniferous compound employed, the dielectric constant of the resulting composition can be varied from that of the polymeric N-vinyl pyrrole compound per so, which averages slightly under 3 in the case of polyvinyl carbazole, to higher values, such as 15, 20, 25 or even higher.

The polymeric N-vinyl pyrrole compounds which have been found to be particularly valuable for use in the present invention. comprise N-vinyl pyrrole compounds containing the pyrrole ring, such as N-vinyl pyrrole, N-vinyl carbazole, N -vinyl tetracarbazole, N-vinyl indole and N-vinyl naphthocarbazole. Polymeric N-vinyl carbazole has been found particularly useful and since this material is commercially available, the present invention will be described particularly in connection with its use, but it should be understood that other N-vinyl pyrrole compounds may be substituted therefor. As is common with most organic polymers, a relatively wide range of polymers of N-vinyl carbazole, as regards molecular weight of the polymer, can be obtained. While it has been found that both the low and high polymers of N-vinyl carbazole are suitable for use in the present invention, it is preferable, as a general rule, to employ a polymeric material containing a substantial amount of reasonably high polymer since, in general, the higher polymers of N-vinyl carbazole have better mechanical strength than does a relatively low polymer. Satisfactory products may be produced in accordance with the present invention from either powdered polyvinyl carbazole or flbered polyvinyl carbazole produced in accordance with United States Patent No. 2,185,789 or mixtures of the same. If desired, various plasticizers may be incorporated in the polymeric N-vinyl carbazole in order to facilitate molding or casting articles from the composition of the present invention and to assist in imparting desired mechanical 3 properties to the finished articles. In general, when employing a plasticizer, it is preferable to employ a non-polar compound since these exert less influence on the electrical properties of the by addition of a non-solvent therefor, for instance, methanol, while agitating= the mixture. When this is done, it has been found that as the N-vinyl pyrrole compound is precipitated it entraps the mass. After the desired amount of titanium compound has been incorporated in the solution of polymeric N-vinyl pyrrole compound and solvent and mixed so as to uniformly distribute the titanate throughout the solution, the solvent may be evaporated so as to leave a solid mixture of polyvinyl N-vinyl pyrrole compound and titanate or ii desired, the solvent may be removed by precipifinished article. Among the plasticizers which 5 dispersed titanium compound. The precipitated have been found to be suitable for use are a parsolids, when filtered off and dried, yield a solid tially hydrogenated terphenyl Monsanto BIB-40 material in which the titanate particles are uni: more fully described on the front cover, vol. 52, formly distributed throughout the polymer. No. 3 of Chemical Industries for March 1943 and The thus-obtained mixture of polymeric in Chemicals and Plastics, 28th ed. published by N-vinyl pyrrole compound and titanium com- Monsanto Chemical Company, page 66, diamylpound can readily be formed into shaped articles naphthalene, tricresyl phosphate and the like. by the usual molding and casting procedures. Small amounts (up to 5 to of materials Thus, the conventional compression or injection like polystyrene also may be used without serious molding procedures may be employed to produce deleterious eifect on the heat distortion point. a wide variety of shaped articles. Such articles The titanium compounds which are employed as films may be produced by usual methods, such as the other components of the composition of the as by casting from a solution of the polymer in present invention comprise titanium dioxide and a volatile solvent, followed by evaporation of the a wide variety of titanates of various materials. solvent. Iitanates containing varying amounts of such In order to better illustrate the present invenmetals as zirconium, tin, beryllium, cadmium, tion, there are given below, in tabular form, a copper, aluminum, boron, cerium, lead tantalum, number of specific examples of dielectric matechro u c a a e nickel, on, and rials produced in accordance with the present intungsten and particularly the alkaline earth vention, the amounts of each ingredient are given metal titanates, such as calcium, cerium, magin parts by weight. The polymer employed in nesium and strontium. and mixtures of the same, these examples was N-vinyl carbazole having a or mixed titanates, such as calcium-barium titandielectric constant of 2.96 and was ground to pass ates, can be made in forms having high dielecmesh screen. The titanates employed were tric constants, greater than 10, and have been ground t pass 100 h r In th found to be suitable for use in the present'invenamples where a. plasticizer was employed, the mation. terial employed was a hydrogenated terphenyl In preparing the novel dielectric materials of derivative (Monsanto HB40) having a distillathe present invention, the polymeric N-vinyl tion range of 353-393 C. and a power factor of pyrrole compound and the titanium com ound 0.2% at 1 me. The titanate was incorporated in may be mixed in any desired manner, so long as 35 the polymer by thorough mechanical mixing in a uniform intimate mixture is obtained. Sat s- Examples 1, 2 and 49, while in Examples 3 and factory products have been produced by thorough 10, the titanate was added to a 20% solution of mechanical mixing of powdered titanates and the polymer in benzene and the polymer precipifinely divided polyvinyl carhazole. However, if tated by the addition of methanol while agitating desired, the powdered titanates may be added to 40 the solution in a Warin v Blender. The precipia solution of polymeric N-vinyl pyrrole comtated solids were then filtered off and dried. All pound in a solvent therefor. In this case, a sufllof the sam les listed in the table were shaped cient amount of volatile solvent may be added by compression molding in a heated die under a to the polyvinyl N-vinyl pyrrole compound to pressureof 5 tons and in the temperature range soften the same so as to form a doughy m ss in of 240-270 C. On ejection from the mold. the which the titanium compound is incorporated by samples were a very light gray in color, but as thorough mixing, or if desired, a larger amount of with the titanates themselves, when exposed to solvent may be employed so as to form a liquid sunlight, they turned pink.

Table Titanate Polymer E5555: 6:32:5 Saml l Amount Kind 2331 gflf fiifii lkc. lmc. Ike. 1 mo.

Carbazole 25 100 0.18 0.10 6.5 6.5 100 1.5 0.17 11.3 11.1 66% 5 0.36 0.10 23.0 21.7 25 0.83 0.69 6.9 6.6 50 100 2.0 1.3 16.8 15.2 66% 05 5 2.5 0.80 31.8 28.8 50 90 10 0.46 0.22 6.4 0.3 00 00 10 0.58 0.18 8.6 as 10 00 -10 0.8l 0.22 12.0 12.1 15 00 10 0.23 17.2

I claim: A heat softenable dielectric composition having a softening point over .100" C., a dielectric constant within the range of 6.3 to 31.8, and

which is moldable under heat and pressure, consisting of an intimate uniform mixture of from 50 to 75 parts by weight of a titanium compound in finely divided form so as to passe 100- tating the polymeric N-vinyl pyrrole compound 7 mesh screen, said titanium compound having a 5 high dieleetricoonstant greater than 10 and being selected from the group consisting of rutile 0 masons crrm The following references are of record in the file of this patent:

6 UNITED STATES PATENTS Number Name Date 2,072,465 Reppe et 9.1. .L Mar. 2, 1937 2,364,790 Hemming Dec. 12, 1944 2,406,319 Brooks et 1 Aug. 27, 1946 

